WO2016155338A1

WO2016155338A1 - Method for preparing butyraldehyde by means of propylene hydroformylation

Info

Publication number: WO2016155338A1
Application number: PCT/CN2015/095603
Authority: WO
Inventors: 丁云杰; 李存耀; 严丽
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2015-04-03
Filing date: 2015-11-26
Publication date: 2016-10-06
Also published as: CN106140301A; CN106140301B

Abstract

A method for preparing butyraldehyde by means of propylene hydroformylation. A heterogeneous catalyst used in the method uses one, two or three of metal Rh, Co or Ir as active components and uses a phosphine-containing organic mixed polymer of a hierarchical porous structure as a carrier, and the phosphine-containing organic mixed polymer is formed by means of copolymerization of an alkylene-containing polydentate organic phosphine ligand and a monodentate organic phosphine ligand. The coordinate bond heterogeneous catalyst is applicable to reactors such as a fixed bed, slurry bed, bubbling bed or trickle bed reactor. The heterogeneous catalyst has good performance in preparing butyraldehyde by means of propylene hydroformylation; butyraldehyde with a high normal/isomeric ratio can be produced; the normal/isomeric ratio can be higher than 25, and the content of propane in the obtained product is lower than 0.1%; the heterogeneous catalyst has good stability, and the separation of the catalyst from a reactant and the product is simple and efficient.

Description

Method for preparing butyraldehyde by hydroformylation of propylene

Technical field

The invention belongs to the field of heterogeneous catalysis and fine chemical industry, and particularly relates to a phosphine-containing organic mixed polymer-metal heterogeneous catalyst, a preparation method thereof and the application thereof in the hydroformylation of propylene to produce butyraldehyde.

Background technique

In recent years, the atomic economic response has become one of the hot spots in green chemistry research. The olefin hydroformylation reaction is a typical atomic economic reaction. It refers to the reaction of olefins with CO and H ₂ to form aldehydes under the action of a catalyst. The atoms in the raw material molecules are converted into products by 100%, and the waste is discharged.

The product of the hydroformylation of olefins is an aldehyde having one more carbon atom of olefins, wherein the normal aldehyde becomes the target product of most hydroformylation reactions due to its large subsequent processing potential, therefore, normal aldehydes and isoforms The proportion of aldehydes (called orthorhombic ratio) is an important indicator of the catalytic performance of the catalyst. In order to increase the ergo ratio of aldehydes, terminal olefins having higher reactivity and normal aldehyde selectivity are commonly used as raw materials in industrial hydroformylation reactions.

Propylene hydroformylation is the most widely used homogeneous catalytic reaction. Its product, isobutyraldehyde, is a colorless liquid at room temperature, flammable, volatile, and has a strong pungent odor. N-butyraldehyde is an important basic organic chemical raw material, mainly used as an intermediate for plasticizers, synthetic resins, rubber accelerators, paints, perfumes, insecticides, etc., and is widely used in polymer materials, construction, papermaking, and textiles. , medicine, pesticides, etc. Isobutyraldehyde is less important than n-butyraldehyde, and its derivatives can be used as monomers for solvents, synthetic fragrances, pharmaceuticals, and certain synthetic resins. Since butyraldehyde can carry out many condensation and addition reactions, as a starting material for the synthesis of various compounds, they occupy a special position in organic synthesis. At present, there are three main production methods of butyraldehyde: acetaldehyde condensation method, carbonylation method and n-butanol dehydrogenation method. At present, most of the technical routes for industrial production of butyraldehyde use oxo synthesis. The acetaldehyde condensation method has been rarely used, and the n-butanol dehydrogenation process is only produced on a small scale. At present, the propylene hydroformylation reaction in the industry still adopts a homogeneous catalytic reaction mode, and the separation of the catalyst from the product and the reactant is difficult, the aldehyde ratio of the product produced by the industrial product is low, and the utilization rate of the raw material is low.

Patent CN1319580A describes a plurality of bidentate phosphite ligands with large steric hindrance, which are hydroformylated with higher olefins of a coordinated homogeneous catalyst such as Rh and Co. The selectivity of the ratio. However, homogeneous catalysts are difficult to recover and ligand synthesis is difficult.

Patent CN1210514A reports a Rh complex catalyst for the hydroformylation of olefins. The Rh complex is a ligand with a multidentate organic nitrogen compound containing at least one tertiary nitrogen group which can be protonated in a weak acid. However, the catalyst is also facing the problem of being difficult to recycle.

In the patent CN102911021A, a composite catalyst system composed of a Rh complex with a biphenyl skeleton or a binaphthyl skeleton bisphosphine ligand, and a triphenylphosphine or a phosphite triphenyl ester monophosphine ligand is used as a catalyst in a linear olefin hydrogen. The normal aldehydes in the formylation reaction have higher selectivity, which reduces the amount of expensive bisphosphine ligands, but the catalytic system is homogeneous.

In the patent CN1986055A, the bisphosphite and triphenylphosphine are also combined with Rh to form a composite catalytic system. In the hydroformylation reaction of propylene, the molar ratio of n-butyraldehyde to isobutyraldehyde is more than 20, which significantly prolongs the double sub- The service life of the phosphate ligand significantly reduces the amount of triarylphosphine, but it is also a homogeneous reaction in nature, and it also faces the problem of difficulty in recycling the catalyst.

Summary of the invention

In order to solve the above problems, it is an object of the present invention to provide a phosphine-containing organic hybrid-metal heterogeneous catalyst and its use in the production of butyraldehyde.

The technical solution of the present invention is:

A phosphine-containing organic polymer-metal heterogeneous catalyst, one, two or three kinds of metals Rh, Co or Ir as active components, a phosphine-containing organic mixture as a carrier, and a metal catalyst in a catalyst The loading is from 0.01 to 10% by weight (preferably from 0.1 to 5% by weight, more preferably from 0.1 to 2% by weight), and the phosphine-containing organic polymer mixture is composed of a polydentate organophosphine ligand containing an olefin group and a monodentate organophosphine group containing an olefin group. The synthesis of a typical vinyl-containing monophosphine diphosphine ligand is described in detail in the literature Chem. Commun., 2014, 50, 11844 and J. Am. Chem. Soc., 2015, 137, 5204.

The olefin group is preferably a vinyl group, and the olefin group-containing polydentate organophosphine ligand is a vinyl group-containing bidentate phosphite organophosphorus ligand, and the olefin group-containing monodentate organophosphine compound The body is a vinyl-containing triphenylphosphine ligand.

The organic hybrid carrier has a multi-stage pore structure, a specific surface area of 100-3000 m ² /g, and contains macropores, mesopores and micropores (wherein macropores account for 5-50% of the total pore volume, mesopores) 5-50% of the total pore volume, micropores account for 5-50% of the total pore volume), pore volume is 0.1-5.0 cm ³ /g, pore size distribution is 0.2-50.0 nm.

The heterogeneous catalyst is a mixture of a polydentate organophosphine ligand and a monodentate organophosphine ligand, and a solvothermal polymerization method is used to initiate polymerization of an olefin group in the organophosphine ligand by a radical initiator to form The multi-stage pore structure contains a phosphine organic mixed polymer as a carrier, the precursor of the active component and the carrier are stirred in an organic solvent, and the active component forms a multi-coordination bond with the exposed P in the phosphine-containing organic polymer carrier, and is evaporated. After the volatile solvent, a heterogeneous catalyst of the coordination bond type is obtained.

The preparation method of the heterogeneous catalyst is:

a) adding a monodentate organophosphine ligand and a polydentate organophosphine ligand, with or without cross-linking, in an organic solvent at 273 to 473 K (preferably 273 to 353 K, more preferably 280 to 300 K) under an inert gas atmosphere And adding a free radical initiator, after mixing, the mixture is stirred for 0.1 to 100 hours, and the preferred stirring time is in the range of 0.1 to 50 hours;

b) Transfer the mixed solution prepared in the step a) to a synthetic autoclave at 273 to 473 K (preferably 323 to 423 K, more preferably 353 to 403 K), and let it stand for 1 to 100 hours by a solvothermal polymerization method under an inert gas atmosphere. (preferably 1 to 50 hours, more preferably 10 to 30 hours) to carry out a polymerization reaction to obtain a phosphine-containing organic mixed polymer;

c) the mixed polymer obtained in the step b) is vacuum-extracted at room temperature to obtain an organic complex containing bare P having a multi-stage pore structure, that is, a support of the heterogeneous catalyst;

d) at 273 to 473 K (preferably 273 to 353 K, more preferably 280 to 300 K), in an inert gas atmosphere, the organic hybrid carrier obtained in the step c) is added to the solvent containing the active component precursor, and stirred at 0.1 to ～ For 100 hours, the stirring time is preferably in the range of 0.1 to 50 hours, after which the organic solvent is removed by vacuum to obtain a heterogeneous catalyst.

The organic solvent described in the step a) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform; the crosslinking agent is styrene, ethylene, propylene, two One or more of vinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-triethynylbenzene; the free radical initiator is cyclohexanone peroxide One or two or more kinds of dibenzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile.

The molar ratio of the monodentate organophosphine ligand to the polydentate organophosphine ligand described in step a) is from 0.01:1 to 100:1 (preferably from 0.1:1 to 10:1, more preferably from 1:1 to 10:1) In the case of addition of a crosslinking agent, the molar ratio of the monodentate organophosphine ligand to the crosslinking agent is from 0.01:1 to 10:1 (preferably from 0.1:1 to 10:1, more preferably from 1:1 to 10: 1) The molar ratio of the monodentate organophosphine ligand to the free radical initiator is from 300:1 to 10:1 (preferably from 100:1 to 10:1, more preferably from 100:1 to 20:1), and polymerization is carried out into an organic mixture. The concentration of the monodentate organophosphine ligand in the organic solvent before the polymer is in the range of 0.01 to 1000 g/L (preferably 0.1 to 100 g/L, more preferably 1 to 100 g/L).

The solvent described in the step d) is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform, and the active component is Rh, Co, Ir One, two or three, wherein the precursor of Rh is Rh(CH ₃ COO) ₂ , RhH(CO)(PPh ₃ ) ₃ , Rh(CO) ₂ (acac), RhCl ₃ ; Co(CH ₃ COO) ₂ , Co(CO) ₂ (acac), Co(acac) ₂ , CoCl ₂ ; The precursor of Ir is Ir(CO) ₃ (acac), Ir(CH ₃ COO) ₃ , Ir ( Acac) ₃ , IrCl ₄ . The metal loading in the catalyst ranges from 0.01 to 10% by weight (preferably from 0.1 to 5% by weight, more preferably from 0.1 to 2% by weight).

A heterogeneous catalyst is used in the production of butyraldehyde. The reaction process is to charge the prepared catalyst into a reactor, and a reaction mixture is introduced. The main components of the mixture are H ₂ and CO, and also contain N ₂ , One or more of He, CO ₂ and Ar, the volume content of H ₂ +CO is 20-70%, the volume ratio of H ₂ /CO is 0.5-5.0, and the raw material propylene also contains propane, ethylene, butene, One or more of butane, the purity is 20 to 100% (usually 20-60%), the reaction temperature is 323 to 573 K, the reaction pressure is 0.1 to 10.0 MPa, and the gas space velocity is 100 to 20000 h ^-1 . The hydroformylation reaction is carried out under a space velocity of 0.01 to 10.0 h ^-1 , and the reactor is a fixed bed, a slurry bed, a trickle bed or a bubbling bed reactor.

The reaction principle of the invention:

The present invention introduces a typical bisphosphine ligand such as an aromatic ring of biphephos into a vinyl (Vinyl) group, that is, a vinyl-containing polydentate organophosphine ligand (Vinyl Biphephos) as a polymerization monomer in an autoclave. Copolymerization with a monodentate organophosphine ligand such as tris(4-vinylphenyl)phosphine to form an organic hybrid having a high surface area and a multi-stage pore structure by solvothermal polymerization, due to the large amount of the organic polymer backbone Exposure of P containing orphaned electrons can form a multi-coordination bond with the active transition metal ion orbit as a catalyst carrier, thereby forming a catalytic active site. In the catalyst, the organophosphine mixed polymer has both the dual functions of a carrier and a ligand, and the active metal component is highly dispersed in the carrier to form a multi-coordination bond with the high concentration of the exposed P. The active metal component is highly dispersed in the monoatomic form in the organophosphine polymer carrier, which greatly improves the utilization efficiency of the metal. Moreover, the active component is not easily lost, the catalyst has a long service life, and the multidentate phosphine ligand in the skeleton has a remarkable steric effect, and the prepared catalyst can significantly improve the stereoselectivity of the product.

The catalyst organic hybrid carrier skeleton provided by the invention contains P, and the organic mixture has the dual functions of the ligand and the carrier; the active metal component can be dispersed in such a large surface area in a single atom or ion manner. In the pore structure organic mixed polymer carrier, the metal utilization efficiency is greatly improved. The monophosphine ligand structural unit in the carrier organophosphine mixed polymer skeleton makes the mixed polymer have a higher P concentration, and easily forms a double or multiple metal-P coordination bond with the active metal component, and the coordination bond has a strong bond. The chemical bonding ability makes the active component not easily lost.

The beneficial effects of the invention are:

The heterogeneous catalyst framework of the present invention contains a multidentate and monodentate organophosphine ligand structural unit, wherein the monodentate organophosphine ligand has a relatively high P on the surface of the mixed polymer, and the polydentate phosphine ligand is With significant steric effect, the active metal atom or ion forms a multi-coordination bond with the exposed P on the mixed polymer, the active component is not easily lost, and the active component of the catalyst is Rh, Co or Ir. Stereoselective, the mixed polymer has a high specific surface area multi-stage pore structure, and has the dual functions of a carrier and a ligand. The active metal component may be highly dispersed in the monoatomic form in the pore or surface of the organic phosphine polymer carrier, thereby improving The utilization efficiency of the metal component.

Such a coordination bond type heterogeneous catalyst is suitable for a reaction process such as a fixed bed, a slurry bed, a bubbling bed and a trickle bed, and the method for producing butyraldehyde by the hydroformylation of propylene provided by the present invention can significantly increase the olefin The conversion rate and the selectivity of the normal aldehyde can solve the problems of long-term stability and selectivity in the heterogeneous process of the olefin hydroformylation reaction, and serious loss of metal components. At the same time, the butyraldehyde produced by the hydroformylation of propylene has a high aspect ratio, reduces the cost of industrial production of propylene hydroformylation, has good catalyst stability, and is simple and efficient in separating reactants and products from catalysts. New industrialization technology for the production of butyraldehyde from propylene hydroformylation.

DRAWINGS

In Figure 1, Figure A shows a typical olefin-based functionalized bisphosphine ligand, and Figure B shows a schematic diagram of Vinyl Biphephos.

Figure 2 is a schematic diagram of the Vinyl Biphephos polymerization technology route.

Figure 3 is a schematic diagram of a typical monodentate organophosphine ligand and a multidentate organophosphine ligand and a crosslinking agent used in the polymerization, wherein L1-L16 is a monodentate organophosphine ligand, and L17-L19 is a multidentate organic Phosphine ligands, L20 and L21 are crosslinkers.

Figure 4 is a ¹ H spectrum of Vinyl Biphephos ligand.

Figure 5 shows the ¹³ C spectrum of the Vinyl Biphephos ligand.

Figure 6 is a ³¹ P spectrum of Vinyl Biphephos ligand.

Figure 7 is a high resolution mass spectrum of Vinyl Biphephos ligand.

Figure 8 is a graph showing the thermogravimetric curve of the catalyst synthesized in Example 1 under a N ₂ atmosphere.

detailed description

The following examples are intended to better illustrate the invention but are not intended to limit the scope of the invention.

The typical monophosphine ligand tris(4-vinylphenyl)phosphine (L1) is synthesized by adding magnesium powder to a 500 ml three-neck round bottom flask with magnetic stirrer in an ice water bath and a nitrogen atmosphere. g, a mixed solution of p-bromostyrene and anhydrous diethyl ether (18.3 g of p-bromostyrene + 100 ml of anhydrous diethyl ether) was added dropwise, and the resulting reaction mixture was stirred at room temperature for 2 hours to complete the reaction. A mixed solution of phosphorus trichloride and anhydrous diethyl ether (4.6 g of phosphorus trichloride + 10 ml of anhydrous diethyl ether) was added dropwise under ice water, and the obtained mixture was stirred at room temperature for 2 hr. 50 ml of deionized water was added to the reaction system under ice-water bath, and the mixture was reacted at room temperature for 2 hours. The organic product obtained by liquid separation and the organic phase is evaporated to remove the solvent, and purified by silica gel column chromatography, using silica gel as a stationary phase and ethyl acetate/petroleum ether (volume ratio 1:10) as a mixed solvent. The eluent is finally obtained as a white powdery solid, which is tris(4-vinylphenyl)phosphine (L1).

The typical bisphosphine ligand Vinyl Biphephos (Fig. 1) is synthesized according to the literature (Org. Lett., 2009, 11, 971).

And B:

In an ice water bath and a nitrogen atmosphere, 7.6 g of A, 50 mg of DMAP (4-dimethylaminopyridine) and 32 mg of acetic anhydride were sequentially added to a 500 ml three-necked flask, and after fully reacting, it was purified by a silica gel column to obtain C:

C and

The reaction is purified by silica gel column to obtain D:

Reducing D with LiH ₄ Al in the presence of KOH in an ethanol solution yields E:

In a 500 ml three-necked flask, 100 ml of toluene, 10 ml of triethylamine, and then 3.5 g of E and 5.0 g of B were added in an ice water bath under a nitrogen atmosphere, and the reaction was sufficiently stirred at room temperature for 2 h. Using silica gel as the stationary phase and a mixed solvent of ethyl acetate/petroleum ether (1:10 by volume) as an eluent, a gray powdery solid was obtained, which was Vinyl Biphephos.

Example 1

In 298 K and an inert gas atmosphere, 10.0 g of Vinyl Biphephos monomer (Fig. 1) was dissolved in 100.0 ml of tetrahydrofuran solvent while 2.5 g of comonomer tris(4-vinylphenyl)phosphine (L1) was added. To the above solution, 1.0 g of a radical initiator azobisisobutyronitrile was added and stirred for 2 hours. The stirred solution was transferred to an autoclave and polymerized by solvothermal polymerization at 373 K under an inert gas atmosphere for 24 h. The solution after the above polymerization was cooled to room temperature, and the solvent was evacuated under vacuum at room temperature to obtain an organic phosphine mixed polymer copolymer copolymerized with Vinyl Biphephos and tris(4-vinylphenyl)phosphine organic monomer. Figure 2 is a schematic diagram of the Vinyl Biphephos organic hybrid carrier polymerization technology route. 3.13 mg of acetylacetone tricarbonyl hydrazine was weighed and dissolved in 10.0 ml of tetrahydrofuran solvent, and 1.0 g of an organic polymer carrier obtained by copolymerization of Vinyl Biphephos and tris(4-vinylphenyl)phosphine was added, and the mixture was inert at 298 K. The mixture was stirred under a gas atmosphere for 24 hours, and then the solvent was evacuated under vacuum at room temperature to obtain a heterogeneous catalyst for hydroformylation of propylene.

Example 2

In Example 2, except that 10.0 g of the comonomer tris(4-vinylphenyl)phosphine (L1) was weighed, instead of 2.5 g of the comonomer tris(4-vinylphenyl)phosphine (L1), the rest The catalyst synthesis process was the same as in Example 1.

Example 3

In Example 3, the synthesis process of the remaining catalyst was the same as in Example 1 except that 0.1 g of a radical initiator azobisisobutyronitrile was weighed instead of 1.0 g of a radical initiator azobisisobutyronitrile.

Example 4

In Example 4, the catalyst synthesis procedure was the same as in Example 1 except that 50.0 ml of tetrahydrofuran solvent was used instead of 100.0 ml of tetrahydrofuran solvent.

Example 5

In Example 5, the catalyst synthesis process was the same as in Example 1 except that 100.0 ml of a dichloromethane solvent was used instead of 100.0 ml of a tetrahydrofuran solvent.

Example 6

In Example 6, the catalyst synthesis process was the same as in Example 1 except that the 393 K polymerization temperature was used instead of the 373 K polymerization temperature.

Example 7

In Example 7, the catalyst synthesis process was the same as in Example 1 except that the polymerization time of 12 h was used instead of the polymerization time of 24 h.

Example 8

In Example 8, the catalyst synthesis process was the same as in Example 1 except that 10.0 g of L20 was further added as a crosslinking agent.

Example 9

In Example 9, the catalyst synthesis process was the same as in Example 1 except that 1.0 g of styrene was further added as a crosslinking agent.

Example 10

In Example 10, 14.05 mg of acetylacetone dicarbonyl cobalt was added in place of acetylacetone tricarbonyl hydrazine in 10.0 ml of tetrahydrofuran solvent, and the rest of the catalyst synthesis process was the same as in Example 1.

Example 11

In Example 11, 2.05 mg of acetylacetone tricarbonyl hydrazine was weighed in place of acetylacetone tricarbonyl hydrazine in 10.0 ml of tetrahydrofuran solvent, and the rest of the catalyst synthesis process was the same as in Example 1.

Example 12

0.5 g of the catalyst prepared above was charged into a fixed bed reactor, and both ends were charged with quartz sand. The hydroformylation reaction was carried out by introducing a reaction mixture (volume ratio H ₂ : CO: C ₃ H ₆ = 1:1:1) at 393 K, 1.0 MPa, and a reaction mixture space velocity of 2000 h ^-1 . The reaction was collected by a collection tank containing 60 ml of cooled deionized water, and the reaction product was all dissolved in the water in the collection tank. The obtained aqueous solution was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector using ethanol as an internal standard. After the water absorption, the reaction tail gas was analyzed online using HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 1.

Example 13

0.5 g of the catalyst prepared in Example 1 was charged into a 50 ml-capacity slurry bed reactor, and 30 ml of valeraldehyde was added as a slurry liquid, and a reaction mixture was introduced (volume ratio H ₂ : CO: C ₃ H ₆ = 1:1:1), hydroformylation reaction was carried out at 393 K, 1.0 MPa, a reaction mixture space velocity of 2000 h ^-1 and a stirring rate of 750 rpm. The reaction was absorbed and collected through a collection tank containing 60 ml of cooled deionized water, and the reaction product and the slurry liquid entrained with the exhaust gas were all dissolved in the water in the collection tank. Others are the same as in Example 12, and the data is shown in Table 1.

Example 14

The catalyst prepared in Example 1 was placed in a 0.5 g fixed bed reactor, and both ends were charged with quartz sand. The micro feed pump pumps propylene at a flow rate of 0.1 ml/min, and the mass flow meter controls the synthesis gas (volume ratio H ₂ :CO=1:1) with a space velocity of 1000 h ^-1 . The propylene and syngas are before entering the reactor. Mix well in the mixer. The hydroformylation reaction was carried out at 373 K, 1 MPa. The reaction was collected in an ice bath cooled collection tank. The obtained liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector using n-propanol as an internal standard. The tail gas from the collection tank was analyzed online using an HP-7890N gas chromatograph equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 1.

Table 1 Specific surface area and propylene reaction data of the catalysts synthesized in Examples 1-13

* The experimental conditions are 120 ° C, 1 MPa, gas distribution (propylene: CO: H ₂ = 1:1:1) space velocity 2000 h ^-1 , all metals are considered to be active sites in TOF calculation. ** indicates that the reaction temperature is 230 ° C, the active component of Example 10 is Co, and the active component of Example 11 is Ir.

Claims

A method for hydroformylation of propylene to produce butyraldehyde, characterized in that the reaction is carried out in the presence of a phosphine-containing organic polymer-metal heterogeneous catalyst, wherein one of the metals Rh, Co or Ir is present in the heterogeneous catalyst Species, two, three as active components, a phosphine-containing organic mixture as a carrier, a phosphine-containing organic mixture from a polydentate organophosphine ligand containing an olefin group and a monodentate organophosphine ligand containing an olefin group Copolymerized, the metal loading in the catalyst ranges from 0.01 to 10% by weight.
The method of claim 1 wherein the functionalized functional group of the olefin-containing polydentate organophosphine ligand and the olefin-containing monodentate organophosphine ligand is preferably a vinyl functional group.
The method according to claim 1 or 2, wherein said olefin-containing polydentate organophosphine ligand is preferably a vinyl-containing bidentate phosphite organophosphorus ligand, said olefin-containing The monodentate organophosphine ligand of the group is a triphenylphosphine ligand containing a vinyl group.
The method according to claim 1, wherein said organic hybrid carrier has a multi-stage pore structure, a specific surface area of 100 to 3000 m 2 /g, a pore volume of 0.1 to 5.0 cm 3 /g, and a pore size distribution. It is 0.2 to 50.0 nm.
The method according to claim 1, wherein the heterogeneous catalyst is a mixture of a polydentate organophosphine ligand and a monodentate organophosphine ligand, and a solvothermal polymerization method is used to initiate the organic reaction via a free radical initiator. The olefin group in the phosphine ligand is polymerized to form a phosphine-containing organic mixture having a multi-stage pore structure as a carrier, and the precursor of the active component and the carrier are stirred in an organic solvent, and the active component and the phosphine-containing organic mixture are mixed. The exposed P in the carrier forms a multiple coordinate bond, and after evaporation of the volatile solvent, a heterogeneous catalyst of a coordination bond type is obtained.
The method of claim 5 wherein:

a) adding a monodentate organophosphine ligand and a polydentate organophosphine ligand in an organic solvent at 273 to 473 K under an inert gas atmosphere, with or without a crosslinking agent, and then adding a free radical initiator, after mixing, The mixture is stirred for 0.1 to 100 hours, and the preferred stirring time ranges from 0.1 to 1 hour;

b) transferring the mixed solution prepared in the step a) to a synthetic autoclave, 273 to 473 K, under an inert gas atmosphere, using a solvothermal polymerization method, and allowing to stand for 1 to 100 hours for polymerization to obtain a phosphine-containing organic compound. Polymer

c) the mixed polymer obtained in the step b) is vacuum-extracted at room temperature to obtain an organic complex containing bare P having a multi-stage pore structure, that is, a support of the heterogeneous catalyst;

d) adding the organic polymer carrier obtained in the step c) to the solvent containing the precursor of the active component in an inert gas atmosphere at 273 to 473 K, and stirring for 0.1 to 100 hours, preferably for a period of 0.1 to 1 hour. Thereafter, the organic solvent was removed by vacuum to obtain a heterogeneous catalyst.
The method according to claim 6, wherein the organic solvent in the step a) is one or more of benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform; The crosslinking agent is one or more of styrene, ethylene, propylene, divinylbenzene, dimethoxymethane, diiodomethane, paraformaldehyde or 1,3,5-triethynylbenzene; The radical initiator is one or more of cyclohexanone peroxide, dibenzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile or azobisisoheptanenitrile;

The solvent described in the step d) is one or more of water, benzene, toluene, tetrahydrofuran, methanol, ethanol, dichloromethane or chloroform, and the active component is Rh, Co, Ir One or more of them, wherein the precursor of Rh is Rh(CH 3 COO) 2 , RhH(CO)(PPh 3 ) 3 , Rh(CO) 2 (acac), RhCl 3 ; the precursor of Co is Co ( CH 3 COO) 2 , Co(CO) 2 (acac), Co(acac) 2 , CoCl 2 ; The precursor of Ir is Ir(CO) 3 (acac), Ir(CH 3 COO) 3 , Ir(acac) 3 , IrCl 4 , the metal loading in the catalyst ranges from 0.01 to 10 wt%.
The method according to claim 6, wherein the molar ratio of the monodentate organophosphine ligand to the polydentate organophosphine ligand in step a) is from 0.01:1 to 100:1, and is added to the crosslinking agent. In the case where the molar ratio of the monodentate organophosphine ligand to the crosslinking agent is from 0.01:1 to 10:1, the molar ratio of the monodentate organophosphine ligand to the radical initiator is from 300:1 to 10:1. Before the organic polymer mixture, the concentration of the monodentate organophosphine ligand in the organic solvent ranges from 0.01 to 1000 g/L.
The method according to claim 1, wherein the reaction process comprises charging the prepared catalyst into a reactor, and introducing a reaction mixture comprising H 2 and CO, and the H 2 /CO volume ratio is 0.5. ～5.0, the raw material is propylene, the reaction temperature is 323-573K, the reaction pressure is 0.1～10.0MPa, the gas space velocity of the mixed gas is 100～20000h -1 , and the propylene liquid hourly space velocity is 0.01～10.0h -1 for the hydroformylation reaction. The reactor is a fixed bed, a slurry bed, a trickle bed or a bubbling bed reactor.
The method according to claim 1, wherein the mixed gas further contains one or more of N2, He, CO2 and Ar, and the volume content of H2+CO is 20 to 70%; One or more of propane, ethylene, butylene, and butane are used, and the raw material propylene has a purity of 20 to 100% (usually 20 to 60%).